After a season with HC Dukla Trencin in the CFIHL, Demitra was selected 227th overall in the 1993 NHL Entry Draft by the Ottawa Senators. He subsequently left Slovakia to join the Senators organization and played three seasons between the NHL and the American Hockey League with Ottawa's minor league affiliate, the PEI Senators. Demitra began the 1996–97 season in a contract holdout with the Senators, resulting in him being traded to the St. Louis Blues in November 1996. After spending the majority of his first season with St. Louis organization in the International Hockey League, he secured a regular roster spot with the Blues in 1996–97. Demitra spent his most successful seasons with St. Louis, being named to three NHL All-Star Games (1999, 2000 and 2002) and winning the Lady Byng Memorial Trophy in 2000. He achieved the 30-goal mark three times and the 90-point mark once as a Blue. Due to the 2004–05 NHL lockout, Demitra returned to HC Dukla Trencin for one season. Upon returning to the NHL the following year, he signed as a free agent with the Los Angeles Kings. After one year with Los Angeles, he was traded to the Minnesota Wild, where he played on the team's top line with winger Marian Gaborik. In July 2008, he became an unrestricted free agent and signed with the Vancouver Canucks. Demitra left the NHL after a two-year stint with the Canucks, joining the KHL's Lokomotiv Yarolsavl; he spent one season with the team.

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Demitra began playing at the men's level with ZTS Dubnica in Czechoslovakia's second-tier league; he recorded 23 points (13 goals and 10 assists) over 28 games. The following season, Demitra joined HC Dukla Trencin of the premier Czechoslovak Extraliga in 1992–93, where he scored 11 goals and 28 points in 46 games. After the season, Demitra was drafted by the Ottawa Senators in the ninth round, 227th overall in the 1993 NHL Entry Draft. He came to be considered one of the best draft steals in NHL history.[4]

Demitra spent most of the 1994–95 with PEI, where in 61 games, Demitra had 26 goals and 74 points to finish third in team scoring. In five playoff games, Demitra had seven assists. Demitra also spent time with Ottawa, as he scored four goals and seven points in 16 games.

He began the 1995–96 season with PEI, as in 48 games, Demitra put up 28 goals and 81 points, which earned him a promotion back to the NHL. With Ottawa, Demitra had seven goals and 17 points in 31 games.

The St. Louis Blues assigned Demitra to the Grand Rapids Griffins of the IHL, where in 42 games, Demitra had 20 goals and 50 points. He was called up to the Blues, and played his first game with the club on March 17, 1997, getting no points in a 3–2 loss to the Phoenix Coyotes. Demitra scored his first two goals with St. Louis on April 3, 1997, scoring twice against Tommy Salo in a 5–5 tie with the New York Islanders. He finished the season appearing in eight games with St. Louis, scoring three goals. Demitra made his NHL playoff debut on April 16, 1997, recording his first playoff point, an assist, in the Blues 2–0 win over the Detroit Red Wings. On April 22, 1997, Demitra scored his first playoff goal, beating Red Wings goaltender Mike Vernon, and added two assists in a 4–0 win over Detroit. Overall, Demitra had a goal and four points in six playoff games.

Demitra made the NHL full-time in 1997–98, as he played in 61 games with St. Louis, scoring 22 goals and 52 points to finish fifth in team scoring. In 10 playoff games, Demitra had three goals and six points.

The 1998–99 was a break-out season for Demitra, as he finished tenth in NHL scoring with 89 points, as he scored 37 goals and added 52 assists in 82 games. Demitra appeared in the 1999 NHL All-Star Game held in Tampa Bay, Florida, scoring a goal for the World team in a 8–6 loss to North America. In the playoffs, Demitra added five goals and nine points in 13 games.

Demitra continued his success in 1999–2000, as he scored 27 goals and 75 points in 71 games to lead the Blues in scoring once again. Demitra played in the 2000 NHL All-Star Game held in Toronto, Ontario, where he scored two goals in a 9–4 World victory over North America. Demitra also scored his first career hat trick, scoring three goals against the Mighty Ducks of Anaheim on February 12, 2000 in a 6–3 Blues victory. Demitra suffered a season ending injury on March 24, 2000, and missed the playoffs. After the season, he was awarded the Lady Byng Memorial Trophy after he accumulated only eight penalty minutes throughout the season.

Injuries cut short Demitra's season in 2000–01 when he appeared in only 44 games with St. Louis. He scored 20 goals and 45 points to finish fifth in team scoring. He scored a hat trick and added two assists for a five point game against the New York Rangers on December 20, 2000 in a 6–3 win. Less than a week later, on December 26, 2000, Demitra had another high scoring game, scoring two goals and four points against the Columbus Blue Jackets in a 5–0 victory. On December 30, 2000, Demitra suffered an injury, however, he came back with the team late in the season, and appeared in 15 playoff games, scoring two goals and six points.

In 2001–02, Demitra was healthy, as he appeared in all 82 games for St. Louis, scoring 35 goals and 78 points to lead the team in scoring and finish seventh in the league scoring race. Demitra had a league high ten game winning goals. He had a four point night against his former team, the Ottawa Senators, on November 27, 2001, scoring two goals and two assists in a 4–2 victory. Demitra appeared in the 2002 NHL All-Star Game held in Los Angeles, California, however, he was held off the scoresheet in a 8–5 World win over North America. In the playoffs, Demitra appeared in 10 games, scoring four goals and 11 points. He had a four point night against the Detroit Red Wings on May 7, 2002, scoring a goal and three assists in the Blues 6–1 victory.

The 2002–03 was Demitra's most productive in the NHL, as he set a career high with 93 points, which placed him sixth in NHL scoring, as Demtira scored 36 goals and 57 assists in 78 games. He had a hat trick and a season high four points on November 29, 2002 in a 7–2 win over the Calgary Flames. In the playoffs, Demtira had two goals and six points in seven games.

Demitra had a disappointing 2003–04 season, scoring 23 goals and 58 points, his lowest totals since his injury plagued 2000–01 season, in 68 games. In the playoffs, Demitra had a goal in five contests. This would be his final season with the Blues, as Demitra left the team fifth in franchise scoring with 493 points in 494 games.

With the 2004-05 NHL lockout cancelling the season, Demitra signed with HC Dukla Trencin of the Slovak Extraliga on September 17, 2004. Demitra led the league in scoring with 28 goals and 82 points in 54 games. Demitra scored four goals and 17 points in 12 playoff games with the team.

On August 2, 2005, Demitra signed a three year, $13.5 million contract with the Los Angeles Kings.[6] On October 5, 2005, Demitra played his first game with the Kings, scoring an assist in a 5–4 loss to the Dallas Stars. The next night, on October 6, 2005, Demitra scored his first goal with his new team, scoring against David LeNeveu of the Phoenix Coyotes in a 3–2 win. Demitra had three four-point games during the season, including one on November 22, 2005 against his former team, the St. Louis Blues in a 6–3 Los Angeles win. Demitra missed 24 games with injuries, including an eye problem, during the season. In 58 games during the season, Demitra had 25 goals and 62 points to finish third in team scoring. On June 24, 2006, Los Angeles traded Demitra to the Minnesota Wild for Patrick O'Sullivan and a first round draft pick in the 2006 NHL Entry Draft.

Demitra joined the Wild and fellow Slovak Marian Gaborik for the 2006–07 season. Demitra played his first game with the Wild on October 5, 2006, recording two assists in a 3–2 win over the Colorado Avalanche. In his next game on October 7, 2006, Demitra scored his first goal with Minnesota, scoring against Tomas Vokoun of the Nashville Predators in a 6–5 victory. Demitra finished the season tied for first in team scoring, as he had 25 goals and 64 points in 71 games. The 64 points were the highest by Demitra since 2002–03. Demitra played in his first playoff game with Minnesota on April 11, 2007, scoring a goal against Ilya Bryzgalov of the Anaheim Ducks in a 2–1 loss. Demitra appeared in five playoff games, scoring a goal and four points.

Demitra was named the captain of the Wild for the month of October 2007[7] as part of the Wild's rotating captaincy to begin the 2007–08 season. Demitra had a tough season, scoring only 15 goals, his lowest total since 1996–97, and 54 points 68 games as he finished fourth in team scoring. In the playoffs, Demitra had a goal and three points in six games. At the end of the season, he became an unrestricted free agent.

On July 10, 2008, Demitra signed a two-year, $8 million contract with the Vancouver Canucks. He played in his first game as a Canuck on October 9, 2008, getting no points in a 6–0 win over the Calgary Flames. In his next game, also against Calgary, Demitra scored his first goal with Vancouver, the game winning overtime goal against Mikka Kiprusoff in a 5–4 win. He finished the season with 20 goals and 53 points in 69 games, finishing fourth in team scoring. Demitra appeared in his first playoff game with Vancouver on April 15, 2009, recording an assist in a 2–1 win over the St. Louis Blues. Demitra scored his first playoff goal with the Canucks on April 30, 2009, scoring against Nikolai Khabibulin of the Chicago Blackhawks in a 5–3 victory. On May 2, 2009, Demitra suffered a shoulder injury against the Blackhawks that would end his season. In six playoff games, Demitra had a goal and three points.

The 2009–10 would be a tough season on Demitra, as he missed most of the regular season with the shoulder injury that occurred in the 2009 playoffs. In 28 games, Demitra had three goals and 16 points, his lowest totals since 1996–97. In the playoffs, Demitra had a three point game against the Los Angeles Kings on April 23, 2010, helping Vancouver to a 7–2 win. Overall, Demitra appeared in 11 playoff games, scoring two goals and six points. After the season, he became an unrestricted free agent. This would mark the end of Demtira's NHL career. He'd played in 847 career games, and scored 304 goals with 464 assists for 768 points.

Demitra joined Lokomotiv Yaroslavl of the KHL on July 15, 2010. In his first season with Lokomotiv, Demitra scored 18 goals and 60 points in 54 games to finish fifth in league scoring. He was named Forward of the Month in January 2011. In 18 playoff games with Yaroslavl, Demitra had six goals and 15 assists for 21 points which placed him second in KHL playoff scoring.

Demitra returned to the team for the 2011–12 season, however, on September 7, 2011, he was killed in a plane crash with all of his teammates.

Demitra was named to Team Slovakia for the 2010 Winter Olympics in his NHL hometown Vancouver. On February 18, 2010, he scored in the seventh round of a shootout to help Slovakia beat Russia in the round robin.[8] In the semi-finals against hosts Canada, Slovakia trailed 3–0 after two periods but rallied with 2 goals in the third period, and Demitra nearly scored with 9 seconds remained in regulation but his shot was stopped by Canucks teammate Roberto Luongo, and the save was dubbed the "Glove from Above".[9] In the bronze medal game against Finland, Demitra assisted twice and scored once in the second period to help his team to a 3–1 lead, though they could not hold on as Finland scored four times (including an empty-net goal) in the third period to claim bronze. Slovakia was ranked in fourth place, as Demitra led the tournament in points with 10 and tied for the lead in assists with seven. His play in the tournament led him to a selection to the all-star team.

The 2011 Lokomotiv Yaroslavl plane crash occurred on September 7, 2011, at 4:02 PM local time, when a Yakovlev Yak-42 passenger aircraft, carrying the entire hockey team of Lokomotiv Yaroslavl of the Kontinental Hockey League (KHL) crashed near Yaroslavl, Russia on its way to Minsk, Belarus, to start the 2011–12 KHL season.[1]

The majority of the club's roster were killed in the plane crash. The airplane caught fire and crashed shortly after take-off, merely 4 kilometers from the Tunoshna airport. Preliminary reports say that 43 of the 45 passengers on board had been killed, including the entire roster and 4 youth players,[10] and that the remaining one (Alexander Galimov) was in critical condition. However, Galimov died a few days later.[11] Demitra's agent, Matt Keator, has confirmed his client's death.[12][13]

Demitra was survived by his wife Maja and two children, Lucas and Zara. He was predeceased by his infant son, Tobias.[14]